Process for the production of alkali metal silicate-organic plastics

ABSTRACT

Polymerable organic compounds and an epoxide compound are emulsified with aqueous alkali metal silicate solutions then polymerized with a catalyst such as a peroxide type catalyst thereby producing an alkali metal silicate organic plastic which may be used as an adhesive, as molding powder or reacted with an organic diisocyanide to produce polyurethane silicate resins and foams.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. patent applicationSer. No. 233,151 filed Feb. 10, 1981, which is a continuation-in-part ofU.S. patent application Ser. No. 146,474 filed May 5, 1980, which is acontinuation-in-part of my U.S. patent application Ser. No. 036,350,filed May 7, 1979, which is a continuation-in-part of my U.S. patentapplication Ser. No. 889,932, filed Mar. 27, 1978, which is acontinuation-in-part of my earlier U.S. patent application Ser. No.663,924, filed Mar. 4, 1976, which is a continuation-in-part of myearlier U.S. patent application Ser. No. 599,000, filed July 7, 1975,now U.S. Pat. No. 4,072,637, which is a continuation-in-part of myearlier U.S. patent application Ser. No. 262,485, filed June 14, 1972,now abandoned, which is a continuation-in-part of my earlier U.S. patentapplication Ser. No. 71,628, filed Sept. 11, 1970, now abandoned.

BACKGROUND OF THE INVENTION

This invention relates to a process for the production of alkali metalsilicate organic plastics by emulsifying a polymerable unsaturatedorganic compound and an organic epoxide compound with an aqueous alkalimetal solution by mixing the polymerable organic compound and an organicepoxide compound with an aqueous solution of alkali metal silicate thenadding a salt-forming compound in the amount up to 10%, based on thealkali metal silicate, preferably an organic acid, while agitatingthereby producing a stable emulsion. A polymerizing catalyst such as aperoxide type catalyst is added to the emulsion thereby producing apoly(alkali metal silicate-polymerable organic compound epoxidecompound) copolymer. In most products an excess amount of the aqueousalkali metal silicate may be used. The inorganic-organic plasticproduced by the process of this invention has greatly improved flameresistance properties.

The polymerization of an alkali metal silicate with a polymerableunsaturated organic compound was illustrated in U.S. patent applicationSer. No. 71,628, filed Sept. 11, 1970, by David H. Blount. The alkalimetal silicate is oxidized by a peroxide initiator then polymerized witha polymerable organic compound. I have discovered that a stable emulsionof an aqueous alkali metal silicate and a polymerable unsaturatedorganic compound may be produced by adding up to 10% by weight,percentage based on weight of the aqueous alkali metal silicatesolution, of a salt forming compound, and mixing with the mixture of theaqueous alkali metal silicate and polymerable compound. This stableemulsion greatly enhances the reaction between the alkali metal silicateand polymerable organic compound. Any suitable polymerable unsaturatedorganic compound may be used in this invention that can be polymerizedin an aqueous alkali metal silicate solution in the presence of aperoxide initiator.

The emulsions of inorganic-organic plastics may be used as an adhesiveon wood, paper, cement, plastics, ceramics, etc., as a coating agent onwood, cement, plastics, ceramics, etc., and may be dried or coagulatedwith a salt forming compound to produce a molding powder which may bemolded by heat and pressure to produce useful objects such as knobs,handles, gears, pipes, toys, etc. The emulsion of inorganic-organicplastics may be further reacted with organic compounds such aspolyisocyanates, isocyanates, epoxide compounds, substituted organiccompounds, water-binding agents and many other compounds. The emulsionof inorganic-organic plastics may be used as a cavity filler, as putty,as a caulking compound, and in producing laminates.

It is accordingly, an object of my invention to provide novelinorganic-organic copolymers. A further object is to provide novelcopolymers which may be used as an adhesive. A further object is toprovide novel copolymers that will react with polyisocyanates to produceuseful resinous and foam products. A further object is to provide aprocess for preparing novel inorganic-organic copolymers. Another objectis to produce emulsions of inorganic-organic copolymers which may beused to produce concrete reinforced and reacted with inorganic-organiccopolymers.

The inorganic-organic plastics may be produced by emulsifying andreacting the following components:

Component (a) an aqueous alkali metal silicate solution;

Component (b) a polymerable unsaturated organic compound;

Component (c) a salt forming compound;

Component (d) an initiator

Component (e) an epoxide compound

Component (a)

Any suitable alkali metal silicate may be used in this invention.Suitable alkali metal silicates include sodium, potassium and lithiumsilicates. The alkali metal silicates are preferred to be in an aqueoussolution. Concentration of 10% to 70% of alkali metal siliates in anaqueous solution or an alkali metal metasilicate pentahydrate which hasbeen melted to produce an aqueous solution. The weight ratio of SiO₂:NaO may vary greatly from 3.75:1 to 1:2. Sodium silicate is thepreferred alkali metal silicate.

Component (b)

Any suitable polymerable unsaturated organic compound may be used inthis invention. Suitable polymerable unsaturated organic compoundsinclude but not limited to vinyl monomers, organic dienes, allylcompounds, unsaturated aliphatic hydrocarbon compounds unsaturatedfluorocarbon compounds and mixtures thereof.

Suitable vinyl monomers include styrene, vinyl acetate acrylates, vinylchloride, vinylidene chloride, acrylonitrile, vinyl toluenes, N-vinylcarbazole, vinyl pyrovidone, vinylidine cyanide, alkyl vinyl ketones,aryl vinyl ketones, methacrylonitrile and mixtures thereof.

Suitable organic dienes include isoprene, chloroprene, butadiene andmixtures thereof.

Suitable allyl compounds include allyl alcohol, methallyl alcohol,phenallyl alcohol, 3-chloropropene, 3-bromopropene, methallyl chlorideand mixtures thereof.

Suitable aliphatic hydrocarbon compound include ethylene, propylene andmixtures thereof.

Suitable acrylate compounds include but are not limited to methylmethacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butylacrylate, pentadecyl acrylate, hexadecyl acrylate, benzyl acrylate,cyclohexyl acrylate, phenyl ethyl acrylate, ethyl methacrylate,methyl-chloroacrylate, 2-chloroethyl acrylate, 1,1-dihydroperfluorobutylacrylate, lauryl acrylate, cyclohexylcyclohexyl methacrylate, allylmethacrylate and mixtures thereof. Acrylic acid compounds which havebeen reacted with an alkali compound may be used in this invention.

Any suitable allyl halide compound having the general formula: ##STR1##wherein R is a hydrogen or a C₁ to C₄ alkyl group and x represents ahalogen atom may be used in this invention. Furthermore, these compoundscontain one olefinic group of which one unsaturated carbon atom containsat least one hydrogen atom per molecule.

Any suitable allyl-type alcohol having the general structure formula:

    CH.sub.2 ═C--OH

may be used in this invention.

Styrene is the preferred polymerable unsaturated organic compound.

Component (c)

Any suitable salt forming compound may be used in this invention, suchas aliphatic carboxylic acids, aliphatic acid anhydrides, aliphaticpolycarboxylic acids, cycloaliphatic carboxylic acids, cycloaliphaticpolycarboxylic acids, aromatic carboxylic acid, aromatic polycarboxylicacids, heterocyclic polycarboxylic acids, aliphatic carboxylic acidanhydrides, aromatic carboxylic acid anhydrides and mixtures thereof.The organic acids may be substituted, e.g. with halogen atoms and may beunsaturated.

Organic polycarboxylic acids are preferred. Adipic acid is the preferredpolycarboxylic acid. It is preferred to use the organic mono-carboxylicacids with polycarboxylic acids.

Examples of suitable aliphatic acids are, but are not limited to, aceticacid, propionic acid, formic acid, butyric acid, valeric acid, caproicacid, undecanoic acid, lauric acid, palmitic acid, stearic acid, acrylicacid, etc.

An example of suitable aliphatic acid anhydrides is acetic anhydride,but examples are not limited to that.

Examples of suitable aromatic acids are, but are not limited to, benzoicacid, para-aminobenzoic acid, alicyclic acid, methyl salicylates, etc.

The polycarboxylic acid may be aliphatic, cycloaliphatic, aromaticand/or heterocyclic and may be substituted, e.g., with halogen atoms andmay be unsaturated; examples include: succinic acid, adipic acid,sebacic acid, suberic acid, azelaic acid, phthalic acid, phthalic acidanhydride, isophthalic acid, tetrahydrophthalic acid anhydride,trimellitic acid, hexahydrophthalic acid anhydride, tetrachlorophthalicacid anhydride, endomethylene tetrahydrophthalic acid anhydride,glutaric acid anhydride, fumaric acid, maleic acid, maleic acidanhydride, dimeric and trimeric fatty acid such as oleic acid,optionally mixed with monomeric fatty acids, dimethylterephthalate andbisglycol terephthalates.

Component (d)

Any suitable organic epoxide compound may be used in this invention.Suitable epoxide compound include ethylene oxide, propylene oxide,butylene oxide, tetrahydrofuran, styrene oxide, trichlorobutylene oxide,epihalohydrins such as epichlorohydrin, epibromohydrin and the like.

Ethylene oxide and propylene oxide and mixtures thereof are thepreferred organic epoxide compounds. Starting components which containreactive hydrogen atoms such as alcohols, e.g., ethylene glycol,propylene-1,3- and -1,2-glycol, trimethylolpropane, 4,4'dihydroxydiphenylpropane, ammonia, ethanolamine, amines, e.g., aniline,ammonia, ethanolamine or ethylenediamine, carbohydrates, e.g., sucrose,dextrose or glucose, may be added to the aqueous alkali metal silicatein an amount up to 10% by weight, percentage based on the reactants,(a), (b), (c) and (d).

Suitable epoxide catalyst may be used with the epoxide compounds such ase.g. organic amines, BF₃ and the like.

Component (e)

Suitable initiators include but are not limited to organic and inorganicperoxides, alkali metal persulfates, ammonium persulfate, redox systems,aliphatic azo compounds, organic and inorganic peroxide with organic andinorganic metal compounds. Suitable peroxide initiators include but arenot limited to hydrogen peroxide and acyl or aryl peroxides such asp-menthane hydroperoxide, ethyl ketone peroxide, benzoyl peroxide,acetyl benzyl peroxide, p-chlorobenzyl peroxide, alkoxy benzoylperoxide, lauroryl peroxide, dibutyryl peroxide, dicaproyl peroxide,crotonyl peroxide, di-tert-alkyl peroxide, methyl amyl ketone peroxide,di-tert-butyl diphosphate peroxide, peracetic acid, cyclohexylhypoperoxide and mixtures thereof. Suitable alkali metal persulfatesinclude ammonium persulfate, potassium persulfate and sodium persulfate.Any suitable commonly known redox systems as known in the arts may beused. Other initiator systems may be used such as peroxides with metalcompounds as activators such as ethyl ketone peroxide with cobaltnaphthenate, potassium persulfate with ferric sulfate or cupric sulfate(0.001 to 0.002 parts by weight per part by weight of the polymerablecompound) and benzoyl peroxide with a tertiary amine activator, such asN,N-dimethyl aniline. The amount of the peroxide initiator needed isquite varied and usually a catalytic amount is sufficient, but may beadded up to 0.5% based on the reaction mixture.

The polymerization may also be initiated by heat or photosensitizerssuch as benzoin, biacetyl, etc., alone or with other initiators incertain reaction.

Surface-active additives (emulsifiers and foam stabilizers) may also beused according to the invention. Suitable emulsifiers are, e.g., thesodium salt of ricinoleic sulphonates or of fatty acids or salts offatty acids with amines, e.g., oleic acid diethylamine or stearic aciddiethanolamine. The commercially available soaps and detergents may beused. Other surface-active additives are alkali metal or ammonium saltsor sulphonic acids, e.g., dodecylbenzene sulphonic acid or dinaphthylmethane disulphonic acids or fatty acids, e.g., ricinoleic acid, or ofpolymeric fatty acids. Surfactants such as sodium dioctylsulfosuccinate, potassium dioctyl sulfosuccinate and dioctyl calciumsulfosuccinate may also be used.

The foam stabilizers used are mainly water-soluble polyester siloxanes.These compounds generally have a polydimethylsiloxane group attached toa copolymer of ethylene oxide and propylene oxide. Foam stabilizers ofthis kind have been described, e.g., in U.S. Pat. No. 3,629,308. Theseadditives are, preferably, used in quantities of from up to 20%, basedon the reaction mixture.

Further examples of surface-active additives, foam stabilizers, cellregulators, stabilizers, flame-retarding substances, plasticizers, dyes,fillers and fungicidal and bacteriocidal substances which are utilizedfor polyurethane foams, but may also be used in this invention, may befound in Kunststoff-Handbuch, Volume VI; published by Vieweg andHochtlen, Carl-Hanser-Verlag, Munich, 1966, e.g., on pages 103 to 113.The halogenated paraffins and inorganic salts of phosphoric acid are thepreferred fire-retardant agents.

SUMMARY OF THE INVENTION

The process for the production of alkali metal silicate organic plasticproducts is simple. It is merely necessary for the components to cometogether; for example, a polymerable unsaturated compound, an organicepoxide compound, an aqueous alkali metal silicate, up to 10% by weightof a salt forming compound, percentage based on the weight of the alkalimetal silicate, and a suitable initiator.

The chemical reaction of this invention may take place in any suitablephysical condition. Ambient pressure is usually satisfactory, but incertain conditions, an elevated or below ambient pressure may be useful.In cases where the polymerable unsaturated compound is a gas it isusually necessary to increase the pressure until the gas is in a liquidstate or decrease the temperature until the gas is in a liquid state oruse a combination of elevated pressure and decreased temperature. Thereactants may be mixed in any suitable manner at any suitabletemperature or pressure.

The preferred method to produce an emulsion of poly(alkali metalsilicate-polymerable unsaturated organic compound-epoxide) copolymer isto thoroughly mix an aqueous alkali metal silicate solution in theamount of 100 parts by weight, a polymerable unsaturated organiccompound in the amount of 5 to 100 parts by weight, an epoxide compoundin the amount of 1 to 100 parts by weight, a salt forming compound inthe amount of up to 10 parts by weight and a catalytic amount of aninitiator to form a stable emulsion then allow the mixture to react for1 to 24 hours at any suitable temperature and pressure.

In an alternate method the aqueous alkali metal solution, salt formingcompound, initiator and optional emulsifiers, foam regulators andfillers are thoroughly mixed then the polymerable unsaturated organiccompound and epoxide compound are added at a suitable temperature andpressure while agitating. The mixture is then allowed to react for 1 to24 hours thereby producing an emulsion of poly(alkali metalsilicate-polymerable unsaturated organic compound-epoxide) copolymer.

The copolymer produced by this invention may be used as a coating agent,as impregnants, as adhesives for wood, paper, etc., may be molded intouseful products such as rods, sheets, blocks, etc., may be furtherreacted with polyisocyanates and used as a reinforcement for waterbinding compounds such as Portland cement.

Any suitable organic polyisocyanate may be used according to theinvention, including aliphatic, cycloaliphatic, araliphatic, aromatic,heterocyclic polyisocyanates and mixtures thereof. Suitablepolyisocyanates which may be in the process of the invention areexemplified by the organic diisocyanates which are compounds of thegeneral formula:

    O═C═N--R--N═C═O

wherein R is a divalent organic radical such as an alkylene, aralkyleneor arylene. Examples of such diisocyanates are:

p,p'-diphenylmethane diisocyanate

phenylene diisocyanate

chlorophenylene diisocyanate

tolylene diisocyanate

m-xylylene diisocyanate

benzidine diisocyanate

naphthylene diisocyanate

tetramethylene diisocyanate

pentamethylene diisocyanate

hexamethylene diisocyanate

decamethylene diisocyanate

thiodipropyl diisocyanate

Other polyisocyanates, polyisothiocyanates and their derivatives may beequally employed. Fatty diisocyanates may be equally employed. Fattydiisocyanates of the following general formula are also suitable:##STR2## where x+y totals 6 to 22 and z is 0 to 2, e.g.,isocyanatostearyl isocyanate.

Other suitable polyisocyanate includetriphenylmethane-4,4',4"-triisocyanate; polyphenyl-polymethylenepolyisocyanate of the kind which may be obtained by anilineformaldehydecondensation followed by phosgenation; perchlorinatedarylpolyisocyanates; phosgenated products of arylaminealdehydecondensates; phosgenated products of arylamineketone condensates;phosgenation products of condensates of anilines alkyl-substituted onthe nucleus such as tolidines, with aldehydes or ketones such asformaldehyde, acetaldehyde, butyraldehyde, acetone and methyl ethylketone and solutions of residual isocyanates in monomericpolyisocyanates of the type produced in the commercial production oftolylene diisocyanate, diphenyl methane diisocyanate or hexamethylenediisocyanate.

Another group of suitable polyisocyanates are so-called modifiedpolyisocyanates, i.e., polyisocyanates containing carbodiimide groups,allophanate groups, isocyanurate groups, urea groups, amide groups,imide groups or biuret groups. Polyisocyanates suitable for modificationin this way include aliphatic, cycloaliphatic, araliphatic, aromatic andheterocyclic polyisocyanates of the type described, for example, by W.Siefken in Justus Liebigs, Annalen der Chemie, 562, pages 75 to 136.Specific examples include: ethylene diisocyanate; 1,4-tetramethylenediisocyanate; 1,6-hexamethylene diisocyanate; 1,12-dodecanediisocyanate; cyclobutane-1,3-diisocyanate; cyclohexane-1,3- and1,4-diisocyanates and mixtures of these isomers;1-isocyanato-3,3,5-trimethyl cyclohexane (U.S. Pat. No. 3,401,190); 2,4-and 2,6-hexahydro tolylene diisocyanate and mixtures of these isomers;hexahydro-1,3- and/or 1,4-phenylene diisocyanate; perhydro-2,4-' and/or-4,4'-diphenylmethane diisocyanate; 1,3- and 1,4-phenylene diisocyanate;2,4- and 2,6-tolylene diisocyanate and mixtures of these isomers;diphenyl methane-2,4'- and/or -4,4'-diisocyanate;naphthylene-1,5-diisocyanate; triphenyl methane-4,4', 4"-triisocyanate;polyphenyl-polymethylene-polyisocyanate of the type obtained bycondensing aniline with formaldehyde, followed by phosgenation anddescribed in British Pat. Nos. 874,430 and 848,671; and perchlorinatedaryl polyisocyanates of the type described in U.S. Pat. No. 3,277,138.

Polyisocyanates of this type are modified in well known manners eitherthermally and/or catalytically by air, water, urethanes, alcohols,amides, amines, carboxylic acids or carboxylic acid anhydrides.Monofunctional low molecular weight alcohols (preferably having 1 to 12carbon atoms, such as methanol, ethanol, n- and isopropyanol, butanol,hexanol, n-octyl alcohol and dodecyl alcohol) may also be used asmodifying agents, providing the urethane groups formed are convertedinto allophanate groups by further reactions with isocyanate present andproviding the functionality of the resulting modified polyisocyanate isnot reduced to an undesirable extent in this way. The modifying agentshould be used in small quantities of less than 10% by weight, based onthe polyisocyanate.

It is generally preferred to use commercially readily availablepolyisocyanates, e.g., tolylene-2,4- and -2,6-diisocyanate and anymixtures of these isomers which is commercially known as ("TDI"),polyphenyl-polymethyleneisocyanates obtained by aniline-formaldehydecondensation, followed by phosgenation which is commercially known as("crude TDI"), and polyisocyanates which contain carbodiimide groups,urethane groups, allophanate groups, isocyanurate groups, urea groups,imide groups or biuret groups ("modified polyisocyanate").

Any suitable polyhydroxyl compound may be used according to theinvention. It is preferred to use organic polyhydroxyl compounds whichcontain from 2 to 8 hydroxyl groups, e.g., polyhydric alcohols,polyesters, polyethers, polythioethers, polyacetals, polycarbonates orpolyester amides containing at least 2, generally from 2 to 8, butpreferably from 2 to 4, hydroxyl groups, of the kind known for producinghomogenous and cellular polyurethanes.

Suitable polyhydric alcohols include, but are not limited to, ethyleneglycol; propylene 1,2- and -1,3-glycol; butylene-1,4- and -2,3-glycol;hexane-1,6-diol; octane 1,8-diol; neopentyl glycol;cyclohexanedimethanol-(1,4-bishydroxymethylcyclohexane);2-methyl-propane-1,3-diol; glycerol; trimethylol propane;hexane-1,2,6-triol; butane-1,2,4-triol; trimethylol ethane;pentaerythritol; quinitol; mannitol and sorbitol; methylglycoside;diethylene glycol; triethylene glycol; tetraethylene glycol;polyethylene glycols; dipropylene glycol; dibutylene glycol andpolybutylene glycols.

Suitable hydroxyl group-containing polyesters may be, for example,reaction products of polyhydric alcohols, preferably dihydric alcohols,with the optional addition of trihydric alcohols, and polybasic,preferably dibasic carboxylic acids. The listed polyhydric alcohols maybe reacted with polycarboxylic acid to produce polyester polymercontaining hydroxyl groups. Instead of the free polycarboxylic acids,the corresponding polycarboxylic acid esters of lower alcohols orpolycarboxylic acid anhydrides or their mixtures may be used forpreparing the polyesters. The polycarboxylic acids may be aliphatic,cycloaliphatic, aromatic and/or heterocyclic and may be substituted,e.g., with halogen atoms, and may be unsaturated. Examples include:succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid,phthalic acid, isophthalic acid, trimellitic acid, phthalic acidanhydride, tetrahydrophthalic acid anhydride, hexahydrophthalic acidanhydride, tetrachlorophthalic acid anhydride, hexahydrophthalic acidanhydride, tetrachlorophthalic acid anhydride, endomethylenetetrahydrophthalic acid anhydride, glutaric acid anhydride, maleic acid,maleic acid anhydride, fumaric acid, dimeric and trimeric fatty acidssuch as oleic acid, optionally mixed with monomeric fatty acids,dimethylterephthalate and bis-glycol terephthalate.

Suitable polyethers with at least 2, generally from 2 to 8, andpreferably 2 to 4, hydroxyl groups may be used according to theinvention and may be prepared, e.g., by the polymerization of epoxidessuch as ethylene oxide, propylene oxide, butylene oxide,tetrahydrofuran, styrene oxide, trichlorobutylene oxide orepichlorohydrin, each with itself, e.g., in the presence of BF₃, or byaddition of these epoxides, optionally as mixtures or successively, tostarting components which contain reactive hydrogen atoms such asalcohols or amines, e.g., water, ethylene glycol, propylene-1,3- and-1,2-glycol, trimethylolpropane, 4,4'-dihydroxydiphenylpropane, aniline,ammonia, ethanolamine or ethylenediamine. Sucrose polyethers such asthose described, e.g., in German Auslegeschriften, Nos. 1,176,358 and1,064,938, may also be used according to this invention. Polyethersmodified with vinyl polymers such as those which may be obtained bypolymerizing styrene or acrylonitrile in the presence of polyethers,(U.S. Pat. Nos. 3,383,351; 3,304,273; 3,523,093 and 3,110,695) andpolybutadienes which contain OH groups are also suitable.

Suitable polyacetals may be obtained from glycols, e.g., diethyleneglycol, triethylene glycol, 4,4'-dihydroxydiphenyldimethylmethane,hexandiol, and formaldehyde. Polyacetals suitable for the invention mayalso be prepared by the polymerization of cyclic acetals.

Suitable polycarbonates with hydroxyl groups may be of the kind, e.g.,those which may be prepared by reacting diols, e.g., propane-1,3-diol;butane-1,4-diol and/or hexane-1,6-diol or diethylene glycol, triethyleneglycol or tetraethylene glycol, with diarylcarbonates, e.g.,diphenylcarbonate or phosgene.

Suitable polythioethers are the condensation products of thiodiglycolwith itself and/or with other glycols, dicarboxylic acids, formaldehyde,aminocarboxylic acids or amino alcohols.

Suitable polyester amines and polyamides include, e.g., thepredominantly linear condensates obtained from polyvalent saturated andunsaturated carboxylic acids or their anhydrides and polyvalentsaturated and unsaturated amino alcohols, diamine, polyamines andmixtures thereof.

Suitable polyhydroxyl compounds which already contain urethane, modifiedor unmodified natural polyols, e.g., castor oil, carbohydrates andstarches may be used in this invention. Additional products of alkyleneoxides with phenolformaldehyde resins or with urea-formaldehyde resinsare also suitable for the purpose of the invention.

Other compounds which contain at least 2 hydrogen atoms capable ofreacting with isocyanates may be used in this invention in place ofpolyhydroxyl compound or with polyhydroxyl compounds such as compoundscontaining amino groups, thiol groups or carboxyl groups.

Examples of these compounds which are to be used according to theinvention have been described, e.g., in High Polymers, Volume XVI,"Polyurethane, Chemistry and Technology", published by Saunders-Frisch,Interscience and Publishers, New York, London, Volume I, 1962, pages 32and 42 and pages 44 to 54; and Volume II, 1964, pages 5 to 6 and 198 to199; and in Kunststoff-Handbuch, Volume VII, Vieweg-Hochtlen,Carl-Hanswer-Verlag, Munich, 1966, on pages 45 to 71.

Water-binding components which may be used, according to the inventioninclude organic or inorganic water-binding substances which have, first,the ability to chemically combine, preferably irreversibly, with waterand, second the ability to reinforce the organic-inorganic end productsof the invention; hold the water chemically bound until water isreleased and extinguishes the fire. The term "water-binding component"is used herein to identify a material, preferably granular orparticulate, which is sufficiently anhydrous to be capable of absorbingwater to form a solid or gel such as mortar or hydraulic cement. Thiscompound may be a mineral or chemical compound which is anhydrous, suchas CaO and CaSO4, but may exist as a partial hydrate. Water-bindingcompoents used are inorganic materials such as hydraulic cements,synthetic anhydrite with silica or burnt lime with silica.

Suitable hydraulic cements are, in particular, Portland cement,quick-setting cement, blast-furnace Portland cement, mild-burnt cement,sulphate-resistant cement, brick cement, natural cement, lime cement,gypsum cement, pozzolan cement and calcium sulphate cement. In general,any mixture of fine ground lime, alumina and silica that will set to ahard product by admixture of water and which combines chemically withthe other ingredients to form a hydrate may be used. The most preferredforms of water-binding agents to be used according to the invention arethose materials which are normally known as cement. In other words, theyare a normally powdered material with which water normally forms a pastewhich hardens slowly and may be used to bind intermixed crushed rock orgravel and sand into rockhard concrete. There are so many differentkinds of cement which can be used in the production of the compositionsof the invention and they are so well known that a detailed descriptionof cement will not be given here; however, one can find such a detaileddescription in Encyclopedia of Chemical Technology, Volume 4, SecondEdition, Published by Kirk-Othmer, pages 684 to 710, as well as in otherwell known references in this field. In particular, pages 685 to 697 ofthe aforementioned Volume 4, Second Edition of Kirk-Othmer'sEncyclopedia, containing a detailed disclosure of the types of cementwhich may be used in the production of the compositions of thisinvention, are incorporated herein be reference.

The ratio of the essential components which lead to the production ofthe polyurethane silicate foams and solid of the invention may vary,broadly speaking, within the following ranges as follows:

(a) 100 to 200 parts by weight of an emulsion of poly (alkalimetal-polymerable unsaturated compound-epoxide compound) copolymer;

(b) 50 to 200 parts by weight of an organic polioisocyanate orpolyisothiocyanate;

(c) up to 150 parts by weight of a polyhydroxyl compound (polyol);

(d) up to 300 parts by weight of a water-binding compound;

(e) up to 20% by weight, based on the reaction mixture, of anemulsifying agent, percentage based on the reaction mixture;

(f) up to 50% by weight of a blowing agent, percentage based on thereaction mixture;

(g) up to 20% by weight of a foam stabilizer, percentage based on thereaction mixture;

(h) up to 10% by weight of an isocyanate initiator (catalyst) percentagebased on the reaction mixture;

(i) up to 50% by weight of a filler, percentage based on the reactionmixture.

The components may be reacted at any suitable temperature or pressure toproduce polyurethane silicate products. The components are preferablymixed at room temperature and pressure, though any suitable temperaturein range of -20° C. to 80° C. may be employed. The chemical reaction isusually exothermic, and the temperature of the mixture is usuallyelevated above 30° C.

To increase the expanded volume of the foams produced by the processaccording to the invention, expanding or blowing agents may be used. Anysuitable blowing agent may be used, including, for example, inertliquids boiling at temperatures of from -25° C. to 50° C. The blowingagents preferably have boiling points of from -15° C. to +40° C.Particularly suitable blowing agents are alkanes, alkenes,halogen-substituted alkanes and alkenes or dialkyl ethers such as, forexample, saturated or unsaturated hydrocarbons with 4 to 5 carbon atomssuch as isobutylene, butane, pentane, petroleum ether, halogenatedsaturated or unsaturated hydrocarbons such as chlorlmethyl, methylenechloride, fluorotrichloromethane, difluorodichloromethane,trifluorochloromethane, chloroethane, trichlorofluoromethane, and C₄-hydrocarbons such as butane, for example, which have proved to be themost suitable. Any suitable highly volatile inorganic and/or organicsubstances may be used as a blowing agent, including those listed above.Additional suitable blowing agents are, for example, acetone, ethylacetate, methanol, ethanol, hexane or diethylether. Foaming can beincreased by adding compounds which decompose at temperatures above roomtemperature to liberate gases such as nitrogen, for example, azocompounds such as azoisobutyric acid nitrile. Other examples of blowingagents are included, for example, in Kunststoff Handbuch, Volume VII,published by Vieweg and Hochtlen, Carl-Hanser-Verlag, Munich 1966, e.g.,on pages 108 and 109, 445 to 453 and 507 to 510. Fine metal powders suchas powdered calcium, magnesium, aluminum or zinc may also be used asblowing agents when an alkali metal silicate is added to the water bythe evolving hydrogen.

The blowing agents may be used in quantities of from up to 50% by weightand preferably in quantities of from 2 to 10% by weight, based on thereaction mixture. The blowing agent is added simultaneously with thecomponents.

Inert gases, especially air, may be used as the blowing agent. Forexample, one of the liquid components can be prefoamed with air and thenmixed with the other components. The components can also be mixed bymeans of compressed air so that foam is directly formed, subsequentlyhardening in molds.

Other substances such as the emulsifiers, activators and foamstabilizers normally used in the production of polyurethane foams canalso be added; however, they are generally not necessary. Silanes,polysiloxanes, polyether polysiloxanes or silyl-modified isocyanates maybe used as foam stabilizers. Examples of foam stabilizers are disclosedin U.S. Pat. No. 3,201,372 at column 3, line 46 to column 4, line 5 andmay be added in an amount up to 20% by weight, percentage based on thereaction mixture.

Activators (catalysts) may optionally be used in the process accordingto the invention. The activators used may be known, per se, e.g.,tertiary amines such as triethylamine; tributylamine;triethylenediamine; N-methyl-morpholine; N-ethyl-morpholine;N-cocomorpholine; N,N,N',N'-tetramethylethylenediamine;1,4-diaza-bicyclo-(2,2,2)-octaine; N-methyl-N'-dimethylaminoethylpiperazine; N,N-benzylamine; bis-(N,N-diethylaminoethyl)-adipate;N,N-diethyl benzylamine; pentamethyl diethylenetriamine; N,N-dimethylcyclohexalamine; N,N,N',N'-tetramethyl-1,3-butanediamine;N,N-dimethyl-phenylethylamine; 1,2-dimethyl imidazole; 2-methylimidazole; hexahydrotriazine derivatives; triethanolamine;triisopropanolaimine; N-methyl-diethanolamine; N-ethyl-diethanolamine;N,N-dimethyl-ethanolamine; and tertiary amine reaction products withalkylene oxides such as propylene oxide and/or ethylene oxide.

Silaamines with carbon-silicon bonds may also be used as catalysts,e.g., those described in German Patent No. 1,229,290, for example,2,2,4-trimethyl-2-silamorpholine or1,3-diethylamineomethyl-tetramethyldisiloxane.

Bases which contain nitrogen such as tetraalkyl ammonium hydroxides,alkali metal hydroxides such as sodium hydroxide, alkali metalphenolates such as sodium phenolate or alkali metal alcoholates such assodium methylate may also be used as a catalyst. Hexahydrotriazines arealso suitable catalysts.

Organic metal compounds may also be used as catalysts according to theinvention, especially organic tin compounds. The organic tin compoundsused are preferably tin salts of carboxylic acids such as tin acetate,tin octoate, tin ethyl hexoate and tin laurate and the dialkyl tin saltsof carboxylic acid such as dibutyl tin diacetate, dibutyl tin dilaurate,dibutyl tin maleate or dioctyl tin diacetate.

Other examples of activators which may be used according to theinvention and details of the activators (catalysts) may be found inKunststoff-Handbuch, Volume VII, published by Vieweg and Hochtlen,Carl-Hanser-Verlag, Munich 1966, e.g., on pages 96 to 102.

The activator is generally used in a quantity of up to 10% by weight,based on the reactants in the mixture, and is added simultaneously withthe other components.

Particularly high quality products are obtained by the process accordingto the invention when the temperature is between 20° C. and about 100°C. When an alkali metal silicate is used with water as the curing agent,the temperature is elevated by the heat produced by the chemicalreaction of NCO-groups and alkali silicate solutions. This results inthe formation of materials which, on the one hand, are hard as stone,but which, on the other hand, are highly elastic and, hence, highlyresistant to impact and breakage.

If the quantity of heat which is liberated during the reaction betweenthe components is not sufficient to obtain optimum properties, mixingcan readily be carried out at elevated temperatures, for example, attemperature of from 30° C. to 100° C. In special cases, mixing can alsobe carried out under pressure at temperatures above 100° C. up to about150° C. in a closed container so that expansion occurs, accompanied byfoam formation, as the material issues from the container.

Generally, production of the foams in accordance with the invention iscarried out by simultaneously mixing the components in any suitablemixer, in a batch-type or continuous mixer, and by allowing theresulting mixture to foam and harden in molds or on suitable substrates,generally outside the mixture. Then after the mixture containingwater-binding agent has expanded and hardened in the mold, water may beadded to the expanded foam by any suitable method, e.g., by sprayingwith water, by steaming, by soaking the foam in water, etc. The water isabsorbed by the foam and reacts with the unreacted water-binding agentto further cure the excess water-binding agent in the cellular solidproduct. The necessary reaction temperature, amounting to betweenpreferably about 0° C. and 200° C. and most preferably to between 20° C.and 130° C., can either be achieved by preheating one or more reactioncomponents before the mixing process or by heating the mixer itself orby heating the reaction mixture prepared after mixing. Combinations ofthese or other procedures for adjusting the reaction temperature are, ofcourse, also suitable. In most cases, sufficient heat is generatedduring the reaction itself so that after the beginning of the reactionor foaming, the reaction temperature can rise to levels of about 100° C.

For any given recipe, the properties of the resulting foams, forexample, their moist density, is governed to some extent by theparameters of the mixing process, for example, the shape and rotationalspeed of the stirrer, the shape of the mixing chamber, etc., and also bythe reaction temperature selected. The foams can have closed or opencells although, in most cases, they are largely made up of closed cells.Densities may be quite varied, but densities of 0.01 and 0.8 g/cc arepreferred.

In cases of high amounts of inorganic material, these foams combine goodflame resistance, insulating properties and low cost of the startingmaterials.

The process according to the invention provides a number of potentialutilities as either porous or homogeneous materials and, accordingly, afew fields of application are outlined by way of the examples whichfollow.

The reaction mixture, with or without a blowing agent, can be coated forexample, onto any given warm, cold or even IR- or HF-irradiatedsubstrates, or after passing through the mixer, can be sprayed withcompressed air or even by the airless process onto these substrates onwhich it can foam and harden to give a filling or insulating coat. Thistype of application may be used for plastering the exterior or interiorof a building or residence with polyurethane silicate concrete toprovide an insulating plaster which is relatively low in cost, has goodflame resistance, good insulating properties and may be color coated orwater-proof coated.

The foaming reaction mixture can also be molded, cast orinjection-molded in cold or heated molds and allowed to harden in thesemolds, whether relief or solid or hollow molds, if desired bycentrifugal casting at room temperature of up to 200° C. or, if desired,under pressure. In this respect, it is quite possible to usestrengthened elements, whether in the form of inorganic and/or organicor metallic wires, fibers, webs, foams, woven fabrics, skeletons, etc.This can be done, for example, by the fiber-mat impregnating process orby processes in which reaction mixtures and strengthening fibers areapplied together to the mold; for example, by means of a spray unit. Themoldings obtainable in this way can be used as structural elements, forexample, in the form of optionally foamed sandwich elements producedeither directly or subsequently by lamination with metal, glass,plastics, etc., in which case the favorable flame behavior of the foamsin their moist or dry form is of particular advantage; however, they canalso be used as hollow bodies, for example, as containers for productsthat may have to be kept moist or cool, active substances, as decorativeelements, as parts of furniture and as cavity fillings. The may be usedin the field of pattern and mold design, and also in the production ofmolds for casting metals.

In one preferred procedure, the components containing a hydraulic cementare mixed in a mixing chamber, then pumped to a mold such as a concreteblock mold, and the mixture expands and hardens. The foamed block isremoved from the mold.

The foams obtainable in this way can be used as insulating materials,cavity fillings, packaging materials, building materials withoutstanding resistance to solvents and favorable flame behavior. Thefoams can also be used as lightweight walls, bricks, blocks, roofshingles or in the form of sandwich elements, for example, with metal,plastic or wood covering layers, in houses, vehicles and aircraftconstruction.

It is also possible to introduce into the foaming reaction mixtures,providing they are still free-flowing, organic and/or inorganic foamableor already foamed particles such as expanded clay, expanded glass, wood,popcorn, cork, hollow beads of plastics like vinyl chloride polymers,polyethylene, styrene polymers or foam particles thereof or even, forexample, polysulphone, polyepoxide, polyurethane, ureaformaldehyde,phenol formaldehyde, polyimide polymers. The reaction mixtures may beallowed to foam through interstitial spaces in packed volumes of theseparticles so as to produce insulating materials which are distinguishedby excellent flame behavior. Combination of expanded clay, glass orslate with the reaction mixture, according to the invention, isespecially preferred.

The foaming mixture containing hydraulic cement may be sprayed in placeof stucco on houses to provide insulation. It may be used inconstruction, engineering, road building, for erecting walls, igloos,seals for filing joints, plastering, flooring, insulation, decorationand as a coating, screen and covering material. The foam can also beused as an adhesive, as mortar or as casting compositions, optionallyfilled with inorganic or organic fillers.

Auxillaries which may, if desired, be used in, or subsequentlyintroduced into, the reaction mixture, such as emulsifiers, surfactants,dispersants, odorants or hydrophobizing substances, enable the propertyspectrum of the foams in either their moist or their dry form to bemodified as required.

The cellular solid products obtained in accordance with the process ofthis invention may be molded. The molds may be made of materialsincluding inorganic and/or organic foamed or unfoamed, materials such asmetals, for example, iron, nickel, fine steel, lacquered orteflon-coated aluminum, porcelain, glass, wood, plastics such as PVC,polyethylene, epoxide resins, ABS, polycarbonate, etc. The foamsobtainable by the invention can be surface-treated or, where they are inthe form of substantially permeable structures such as open-cell foamsor porous materials, can even be treated by centrifuging vacuumtreatment Similarly, the dry molded products can also be after-treatedby rinsing or impregnating with aqueous or non-aqueous acid, neutral orbasic liquids or gases such as inorganic or organic acids, ammonia,amines, organic or inorganic salt solutions, lacquer solutions,solutions of polymerizable or already polymerized monomers, dyesolutions, galvanizing baths, solutions of catalysts or catalystpreliminary stages, odorants and the like.

The cellular solid products produced by the invention can besubsequently lacquered, metallized, coated, laminated, galvanized,subjected to vapor deposition, bonded or flocked in their moist or dryform or in impregnated form. The cellular solid products can be furtherprocessed for example, by sawing, milling, drilling, planing, polishingand other machining techniques. The cellular solid products may bemodified in their properties by thermal after-treatment, oxidationprocesses, hot-pressing, sintering processes or surface melting or otherconsolidation processes.

The new cellular solid products are particularly suitable for use asstructural materials because they show tensile and compressive strength,are tough, rigid and, at the same time, elastic. They show highpermanent dimensional stability when hot, are substantiallynon-inflammable, and have excellent heat-insulating and sound-insulatingproperties. High quality, lightweight structural panels and complicatedmoldings may be made, optionally under pressure, from the products ofthis invention. It is also possible, by adopting a suitable procedure,to produce molding with an impervious outer skin. When a technique offoaming in the mold under pressure is employed, molded parts with densemarginal zones and completely non-porous, smooth surfaces are obtained.

Fillers in the form of particulate or powdered materials can beadditionally incorporated into the mixtures of organic polyisocyanatesand poly-(alkali metal silicate-polymerable unsaturated organiccompounds) copolymers for a number of applications.

Suitable fillers include solid inorganic or organic substances, forexample, in the form of powders, granulates, wire fibers, dumb-bells,crystallites, spirals, rods, beads, hollow beads, foam particles, webs,pieces of woven fabric, knot fabrics, ribbons, pieces of film, etc., forexample, of dolomite, sand, crushed rocks, chalk, alumina, asbestos,iron oxide, aluminum oxide and oxide hydrates, zeolites, basalt wool orpowder, glass fibers, C-fibers, graphite, carbon black, Al-, Fe-, Cu-,Ag-powder, molybdenum sulphite, steel wool, bronze or copper cloth,silicon powder, expanded clay particles, hollow glass beads, glasspowder, lava and pumice particles, wood chips, sawdust, cork, cotton,straw, jute, sisal, hemp, flax, rayon, popcorn, coke, particles offilled or unfilled, foamed or unfoamed, stretched or unstretched organicpolymers, including plastics and rubber waste. Of the numbers ofsuitable organic polymers, the following, which can be present in theform of foam particles, granulate, powder, hollow beads, beads, foamableor unfoamed particles, fibers, ribbons, woven fabrics, webs, etc., arementioned purely by way of example: polystyrene, polyethylene,polypropylene, polyacrylonitrile, polybutadiene, polyisoprene,polytetrafluoroethylene, aliphatic and aromatic polyesters,melamine-urea or phenol resins, polyacetal resins, polyepoxides,polyhydantoins, polyureas, polyethers, polyurethanes, polyimides,polyamides, polysulphones, polycarbonates, and, of course, any copolymeras well. Inorganic fillers are preferred.

Generally, the composite materials according to the invention can befilled with considerable quantities of fillers without losing theirvaluable property spectrum. The amount of fillers can exceed the amountof the components. In special cases, the inorganic-organic components ofthe present invention act as a binder for such fillers.

A high-boiling aromatic ester plasterizer such as a benzoate orphthalate ester, or polyester benzoate, e.g., dipropylene glycolbenzoate, dodecyl phthalate or propylene glycol phthalate, may be addedin certain applications to the polyisocyanate or poly(alkali metalsilicate-polymerable organic compound-epoxide) copolymer in an amount upto 50% by weight, based on the polyisocyanate or poly(alkali metalsilicate-polymerable organic compound-epoxide) copolymer depending onwhich the plasterizer is added to.

A resin extender may be added, in certain applications, (in an amount upto 50% by weight) to the polyisocyanate such as coal tar, e.g., AlliedChemical 439 oil, a high-boiling coal tar distillate having a Brookfieldviscosity at 160° F. of 14 to 33 c.p., mineral oil and poly-alphamethylstyrene, e.g., Dow Resin 276-V2. Other types of polymer may also beadded to the polyisocyanate.

DESCRIPTION OF PREFERRED EMBODIMENTS

My invention will be illustrated in greater detail by the specificexamples which follow, it being understood that these preferredembodiments are illustrative of, but not limited to, procedures whichmay be used in the production of alkali metal silicate organic plasticproducts. Parts and percentages are by weight unless otherwiseindicated.

EXAMPLE 1

Sodium metasilicate pentahydrate is melted to produce an aqueoussolution of sodium metasilicate, then mixed with an equal amount byweight of an equal mixture of propylene oxide and styrene; then 5% byweight of adipic acid, percentage based on weight of sodium metasilicateare added and thoroughly mixed thereby producing a stable emulsion ofstyrene and propylene oxide in the aqueous solution of sodiummetasilicate. About 0.1% by weight of benzoyl peroxide percentage basedon weight of reactant and about 0.05% cobalt naphthenate is thoroughlymixed in the emulsion. The mixture is polymerized in 1 to 24 hours toproduce an emulsion of poly(sodium silicate-styrene-propylene oxide)copolymer.

The emulsion may be diluted with water or dilute sodium hydroxidesolution to obtain the desired viscosity, the desired color pigmentadded, then painted on new or cured concrete floor, stairs or blocks fora coating agent to improve water resistance and for decoration.

EXAMPLE 2

About 30 parts by weight of an aqueous sodium silicate solutioncontaining 14.7% Na₂ O and 29.4% SiO₂ by weight, 20 parts by weight ofstyrene, 5 parts by weight of propylene oxide, 0.5 parts by weight ofthe sodium salt of ricinoleic sulphonates and 1 part by weight ofbenzoic acid are thoroughly mixed and emulsified; then 0.1 part byweight of potassium persulfate, 0.01 part by weight of ferric sulfateand 0.1 part by weight of benzoyl peroxide is added to the emulsion andthoroughly mixed at ambient temperature (24° C.) and pressure. Themixture is polymerized in 1 to 24 hours thereby producing a poly(sodiumsilicate-styrene-propylene oxide) copolymer emulsion.

EXAMPLE 3

Poly(sodium silicate-vinyl acetate-propylene oxide) copolymer emulsionis produced by mixing and reacting the following components for 1 to 24hours:

(1) 30 parts by weight of an aqueous sodium silicate solution containing19.7% Na₂ O and 31.5% SiO₂ by weight;

(2) 15 parts by weight of vinyl acetate;

(3) 10 parts by weight of propylene oxide;

(4) 0.2 parts by weight of p-menthane hyperperoxide, 0.02 parts byweight of cupric sulfate and 0.8 parts by weight of testdodecylmercaptan.

The emulsion is diluted with a dilute aqueous sodium hydroxide solutionuntil the desired viscosity is obtained then used as a binder by mixingwith cellulose fibers. The wet cellulose fibers are placed on a smallsheet-making machine thereby producing handsheets which are then firedat about 160° F.

EXAMPLE 4

About 30 parts by weight of an aqueous sodium silicate solutioncontaining 18% Na₂ O and 36% SiO₂ by weight, 10 parts by weight ofacrylonitrile, 10 parts by weight of propylene oxide, 1 part by weightof glyceral, 1 part by weight of para aminobenzoic acid, 0.01 part byweight of ferric sulfate are thoroughly mixed thereby producing a stableemulsion. The mixture is reacted at ambient temperature and pressure for1 to 24 hours thereby producing a poly(sodiumsilicate-acrylonitrile-propylene oxide) copolymer emulsion.

EXAMPLE 5

About 50 parts by weight of an aqueous sodium silicate solutioncontaining about 10% Na₂ O and 25% SiO₂ by weight, 25 parts by weight ofmethyl methacrylate, 10 parts by weight of propylene oxide, 2 parts byweight of phthalic anhydride, 5 parts by weight of sodium hydroxide and0.5 parts by weight of benzoyl peroxide are thoroughly mixed therebyproducing an emulsion. The mixture is reacted at ambient temperature andpressure for 1 to 24 hours thereby producing a poly(sodiumsilicate-methyl methacrylate-propylene oxide) copolymer emulsion.

Other acrylate compounds may be used in place of methyl methacrylatesuch as methylacrylate, ethyl acrylate, propylacrylate, butyl acrylate,pendecyl acrylate, hyxodecyl acrylate, benzyl acrylate, cyclohexylacrylate, phenyl ethyl acrylate, ethyl methacrylate,methylα-chloroacrylate, 2-chloroethyl acrylate,1,1-dihydroperfluorobutyl acrylate, lauryl acrylate,cyclohexylcyclohexyl methacrylate, methacrylate, allyl methacrylate,ethylene methacrylate, n-butyl methacrylate and the like and mixturesthereof.

The emulsion may be used as an adhesive by applying to two pieces ofboards then placing them together to dry.

EXAMPLE 6

About 50 parts by weight of an aqueous sodium silicate solutioncontaining about 10% Na₂ O and 20% SiO₂ by weight, 40 parts by weight ofisoprene, 5 parts by weight of propylene oxide, 2 parts by weight ofadipic acid, 0.5 parts by weight of potassium persulfate and 0.01 partby weight of ferric sulfate are thoroughly mixed thereby producing astable emulsion. The mixture is reacted at a temperature and pressure tokeep the temperature just below the boiling temperature of isoprene for1 to 24 hours thereby producing a poly (sodium silicate-isoprenepropylene oxide) copolymer emulsion.

Other organic dienes may be used in place of isoprene such aschloroprene, butadiene and mixtures thereof, at a temperature andpressure where the organic diene is in a liquid state.

The emulsion may be used in construction as a caulking compound aroundwindows and doors.

EXAMPLE 7

About 50 parts by weight of an aqueous sodium silicate solutioncontaining 12.45% Na₂ O and 32.1% SiO₂ by weight, 20 parts by weight ofvinyl pyrrolidone, 15 parts by weight of propylene oxide, 0.05 parts byweight of hydrogen peroxide (aqueous solution containing about 30% H₂O₂), 0.01 part by weight of cupric sulfate and 1 part by weight ofacetic acid are thoroughly mixed thereby producing an emulsion. Themixture is polymerized in 1 to 24 hours thereby producing a poly(sodiumsilicate-vinyl pyrrolidone-propylene oxide) copolymer emulsion.

EXAMPLE 8

About 50 parts by weight of an aqueous potassium silicate solutioncontaining about 10% K₂ O and 15% SiO₂ by weight, 10 parts by weight ofallyl chloride, 20 parts by weight of propylene oxide, 2 parts by weightof adipic acid, 1 part by weight of calcium salt of stearic acid, 0.05parts by weight of potassium persulfate and 2 parts by weight of adipicacid are thoroughly mixed at ambient temperature and pressure therebyproducing a stable emulsion. The mixture is polymerized in 1 to 24 hoursthereby producing a poly(potassium silicate-allyl chloride-propyleneoxide) copolymer emulsion.

The emulsion may be used as an adhesive for glueing paper together ormay be reacted with organic diisocyanates to produce foam forinsulation.

Other allyl halide compounds may be used in place of allyl chloride suchas allyl bromide, methallyl chloride, methallyl bromide, and the like.

EXAMPLE 9

About 50 parts by weight of an aqueous sodium silicate solutioncontaining about 10% Na₂ O and 15% SiO₂ by weight, 0.05 parts by weightof potassium persulfate, 0.1 parts by weight of calcium octanoate, 0.2parts by weight of lithium stearate and 2 parts by weight of adipic acidis added to a 2 quart capacity reactor equipped with a stirrer and apressure gauge. The closed reaction was swept free of air with anitrogen purge. About 30 parts by weight of vinyl chloride monomer and10 parts by weight of ethylene oxide was slowly added to the reactorwhile agitating at about 50° C. and at a pressure between 7 to 8 kg percm² for about 12 hours thereby producing a poly(sodium silicate-vinylchloride-ethylene oxide) copolymer emulsion.

EXAMPLE 10

About 50 parts by weight of an aqueous sodium silicate solutioncontaining about 15% Na₂ O and 25% SiO₂ by weight, 10 parts by weight ofpropylene oxide, 2 parts by weight of adipic acid, 0.2 parts by weightof sodium stearate and 0.1 part by weight of benzoyl peroxide are mixedthen added to an autoclave and a temperature of about 50° C. ismaintained at a pressure between 7.0 and 7.1 kg per cm². Vinyl chloridemonomer is slowly added while agitating over a period of 7 to 10 hoursuntil the emulsion contains about 30% vinyl chloride polymerized withthe sodium silicate and propylene oxide thereby producing an emulsion ofpoly(sodium silicate-vinyl chloride-propylene oxide) copolymer.

The emulsion may be appled to paper and used as an adhesive or used as acoating agent for wood.

EXAMPLE 11

About 50 parts by weight of an aqueous sodium silicate solutioncontaining about 14.7% Na₂ O and 29.4% SiO₂ by weight, 2 parts by weightof para-aminobenzoic acid, 0.5 parts by weight of sodium laurylsulphate, 0.05 parts by weight acetyl peroxide, 0.05 parts by weight ofbenzoyl peroxide, 10 parts by weight of propylene oxide, 2 parts byweight of surcose, and 30 parts by weight of vinylidene chloride aremixed thoroughly thereby forming a stable emulsion. The mixture ispolymerized in 1 to 24 hours thereby producing a poly(sodiumsilicate-vinylidene chloride-propylene oxide) copolymer emulsion.

Other vinyl monomers may be used in place of vinylidene chloride such asdivinyl benzenes, n-vinyl carbazole, arylvinyl ketones, alkyl vinylketones, vinyl pyridines, vinyl pyrrolidone, vinyl acetate,acrylonitrile, methacrylonitrile, styrene, methacrylate and mixturesthereof.

Other organic epoxide compounds may be used in place of propylene oxidesuch as, styrene oxide, epichlorohydrin, butylene oxide,tetrahydrofuran, trichlorobutylene oxide and the like.

EXAMPLE 12

About 50 parts by weight of an aqueous sodium silicate solutioncontaining about 13% Na₂ O and 25% SiO₂ by weight, 2 parts by weight ofphthalic anhydride, 10 parts by weight of acrylonitrile, 5 parts byweight methallyl chloride, 10 parts by weight of propylene oxide, 0.5parts by weight of potassium fatty acid soap, 0.05 parts by weight ofpotassium persulfate, 0.05 parts by weight of benzoyl peroxide and 0.01parts by weight of cupric sulfate are thoroughly mixed thereby forming astable emulsion. The mixture is occasionally agitated at ambienttemperature and pressure and is polymerized in 1 to 24 hours therebyproducing a poly(sodium silicate-methallylchloride-acrylonitrile-propylene oxide) copolymer emulsion.

Other vinyl monomers may be used in place of acrylonitrile such asmethyl methacrylate, styrene divinyl benzenes, methacrylonitrite,n-vinyl carbozole, aryl vinyl ketones, alkyl vinyl ketones, vinylpyridines, vinyl pyrrolidone, vinyl acetate, ethylacrylate and the like.

Other allyl compound may be used in place of methallyl chloride such asallyl chloride, allyl alcohol, allyl bromide and the like.

EXAMPLE 13

About 50 parts by weight of an aqueous sodium silicate solutioncontaining 10% by weight Na₂ O, and 20% by weight SiO₂, 2 parts byweight of adipic acid, 10 parts by weight of propylene oxide, 1 part byweight sodium salt of fatty acids and a redox system containing 0.006parts by weight of potassium persulfate and 0.1 parts by weight ofdodecyl mercaptan are mixed and cooled to about -5° C. in a closedsystem; then 20 parts by weight of butadiene in a liquid state at about-5° C. added to the mixture and thoroughly mixed thereby producing astable emulsion. The mixture is polymerized in 1 to 24 hours to producean emulsion of poly(sodium silicate-butadiene-propylene oxide)copolymer.

The emulsion may be applied to two wood (board) surfaces then the woodis placed together and the emulsion acts as a strong adhesive when driedin 24 hours.

EXAMPLE 14

About 50 parts by weight of an aqueous sodium silicate solutioncontaining about 10% Na₂ O and 15% SiO₂, 1 part by weight of adipicacid, 20 parts by weight of butadiene, 5 parts by weight of propyleneoxide, 0.5 parts by weight of sodium salt of fatty acids, 0.05 to 0.1parts by weight of ferric sulfate, 0.1 parts by weight of hydrogenperoxide, 0.01 parts by weight of benzoxyl peroxide and 0.1 parts byweight of lauryl mercaptan are mixed in a closed system at ambient to50° C. while agitating at about 0.40 to 6 psiq for 30 to 120 minutes;then the mixture is heated to 70° to 100° C. at ambient pressure for 10to 30 minutes. The reaction is complete within 24 hours therebyproducing an emulsion of poly(sodium silicate-butadiene-propylene oxide)copolymer.

The emulsion may be used as a caulking compound in construction.

EXAMPLE 15

About 60 parts by weight of an aqueous sodium silicate solutioncontaining about 15% Na₂ O and 20% SiO₂ by weight, 20 parts by weight ofbutadiene, 10 parts by weight of styrene, 10 parts by weight ofacrylonitrile, 5 parts by weight of propylene oxide, 2 parts by weightof adipic acid, 3 parts by weight of potassium salt or fatty acids, 1part by weight of trisodium phosphate dodecahydrate, 0.2 parts by weightof diethylenetriamine, 0.2 parts by weight of diethylenetriamine, 0.2parts by weight of p-menthane hydroperoxide, 0.005 parts by weight offerrous sulfate and 0.3 parts by weight of tert-dodecyl mercaptan areadded to a closed system and are mixed thoroughly under 45 to 60 psiqand at 5° C. to 50° C. in a closed system, thereby producing a stableemulsion. The reaction is complete within 24 hours thereby producing anemulsion of poly(sodiumsilicate-butadiene-styrene-acrylonitrile-propylene oxide) copolymer.

The emulsion may be dried, then powdered, then molded by heat andpressure into useful products such as sheets, tubes, knobs, etc.

EXAMPLE 16

About 50 parts by weight of an aqueous sodium silicate solutioncontaining about 10% by weight of Na₂ O and 20% by weight of SiO₂, 10parts by weight of isoprene, 10 parts by weight of allyl chloride, 10parts by weight of vinylidine chloride, 5 parts by weight of propyleneoxide, 2 parts by weight of sodium salt of fatty acids, 2 parts byweight of sodium salt of fatty acids, 2 parts by weight of adipic acid,0.5 parts by weight of benzoyl peroxide and 0.01 N,N-dimethyl anilineare thoroughly mixed thereby producing a stable emulsion at ambienttemperature and pressure. The reaction is complete in 1 to 24 hoursthereby producing an emulsion of poly(sodium silicate-allylchloride-isoprene-vinylidine chloride propylene oxide) copolymer.

The emulsion may be painted in wood and used as an adhesive or coatingagent.

EXAMPLE 17

About 60 parts by weight of an aqueous sodium silicate solutioncontaining about 15% by weight of Na₂ O and 25% by weight of SiO₂, 5parts by weight of chloroprene, 5 parts by weight of allyl alcohol, 5parts by weight of vinylbenzyl alcohol, 5 parts by weight of styrene, 5parts by weight of propylene oxide, 1 part by weight of citric acid, 1part by weight of aminobenzoic acid, 2 parts by weight of sodium salt offatty acids, 0.1 parts by weight of hydrogen peroxide, 0.05 parts byweight of benzoyl peroxide and 0.1 part by weight ofazo-bisisobutyronitrile, are thoroughly mixed in a closed system therebyproducing a stable emulsion. The emulsion is heated to 80° to 100° C.under autogenous pressure for 1 to 24 hours thereby producing anemulsion of poly(sodium silicate-unsaturated organic compound-propyleneoxide) copolymer.

The emulsion may be used as caulking material in construction to sealaround doors and window.

EXAMPLE 18

About equal parts by weight of a polyisocyanate listed below and anemulsion of poly(sodium silicate-unsaturated compound-epoxide compound)copolymer as produced in the Examples listed below are thoroughly mixedat ambient temperature and pressure and reacts within 15 seconds to 5minutes to produce a polyurethane silicate resinous product.

    ______________________________________                                                 Emulsion                                                                      Produced in                                                          EXAMPLE  Example No.                                                                              Polyisocyanate                                            ______________________________________                                        a        Example 1  polyphenyl-polymethylene-                                                     isocyanates with an isocyanate                                                content of about 5% by weight.                            b        Example 2  tolylene diisocyanate                                     c        Example 3  p,p' diphenylmethane                                                          diisocyanate                                              d        Example 4  polyphenyl-polymethylene-iso-                                                 cyanates with an isocyanate con-                                              tent of about 23% by weight.                              e        Example 5  polyphenyl-polymethylene-                                                     polyisocyanate with an iso-                                                   cyanate content of about 2.5%                                                 by weight                                                 f        Example 6  4,4'-phenylmethylene diisocya-                                                nate.                                                     g        Example 7  polyphenyl-polymethylene-                                                     isocyanates with an isocyan-                                                  ate content of about 23% by                                                   weight.                                                   h        Example 8  polyphenyl-polymethylene-                                                     isocyanates with an iso-                                                      cyanate content of about                                                      15% by weight.                                            i        Example 9  polyphenyl-polymethylene-                                                     isocyanate with an isocya-                                                    nate content of about 7%                                                      by weight.                                                j        Example 10 Tolylene diisocyanate                                     k        Example 11 4,4'-phenylmethylene diiso-                                                   cyanate.                                                  l        Example 12 isocyanate-terminated poly-                                                   ethylene (NCO content 19%                                                     by weight).                                               m        Example 13 polyphenyl-polymethylene-                                                     isocyanates with an isocya-                                                   nate content of about 18%                                                     by weight.                                                n        Example 14 tolylene diisocyanate                                     o        Example 15 4,4'-phenylmethylene                                                          diisocyanate.                                             p        Example 16 Sulphonated polyphenyl-                                                       polymethylene-polyisocyanate.                             q        Example 17 Residue of tolylene                                                           diisocyanate distilla-                                                        tion (18% by weight of                                                        NCO)                                                      r        Example 18 25% solution of toly-                                                         lene diisocyanate re-                                                         sidue polyphenyl-poly-                                                        methylene-polyisocyanate                                                      (NCO content 30%)                                         ______________________________________                                    

EXAMPLE 19

About equal parts by weight of an isocyanate-terminated polyurethaneprepolymer listed below and an emulsion of poly(sodiumsilicate-unsaturated compound-epoxide compound) copolymer as produced inthe examples listed below are thoroughly mixed at ambient temperatureand pressure. The mixture reacts within 15 seconds to 5 minutes toproduce a polyurethane silicate resinous product.

    ______________________________________                                               Emulsion                                                                      Produced                                                               EX-    In Example                                                                              Isocyanate-terminated polyurethane                           AMPLE  No.       Prepolymer                                                   ______________________________________                                        a      Example 1 isocyanate-terminated polyethylene                                            ether (NCO content 19% by weight)                            b      Example 2 isocyanate-terminated polypropylene                                           ether (NCO content 22% by weight)                            c      Example 3 isocyanate-terminated polyester                                               (NCO content 11% by weight)                                  d      Example 4 isocyanate-terminated polybutadiene                                           (NCO content 15% by weight)                                  e      Example 5 isocyanate-terminated polyisocyanate                                          silicate (NCO content 12% by weight)                         f      Example 6 isocyanate-terminated polysulfide                                             (NCO content 15% by weight).                                 ______________________________________                                    

EXAMPLE 20

About 50 parts by weight of a polyisocyanate listed below and 60 partsby weight of an emulsion of poly(sodium silicate-unsaturated organiccompound-epoxide compound) copolymer as produced in the example listedbelow, 5 parts by weight of trichlorotrifluoroethane, 0.5 parts byweight of triethylenediamine, 0.001 parts by weight of tin octoate arethoroughly mixed. The mixture begins to expand in 15 to 120 seconds to 3minutes thereby producing a foamed polyurethane resinous product.

    ______________________________________                                               Emulsion                                                                      Produced                                                               EX-    in Example                                                             AMPLE  Number    Polyisocyanate                                               ______________________________________                                        a      Example 1 polyphenyl-polymethylene-isocyanates                                          with an NCO content of about 12%.                            b      Example 2 tolylene diisocyanate                                        c      Example 3 4,4'-phenylmethylene diisocyanate                            d      Example 4 4,4'-phenylmethylene diisocyanate                            e      Example 5 sulphonated polyphenyl-polymethylene-                                         polyisocyanate                                               f      Example 6 residue of tolylene diisocyanate distil-                                      lation (approximately 18% by weight of                                        NCO)                                                         g      Example 7 Equal parts by weight of tolylene diiso-                                      cyanate and polyphenyl-polymethylene-                                         isocyanates with an isocyanate content                                        of 2.5%.                                                     ______________________________________                                    

The foamed polyurethane silicate may be used to produce constructionpanels, lightweight building blocks, foamed on walls for insulation,door cores and as decorative items.

EXAMPLE 21

About 50 parts by weight of polyphenyl-polymethylene-isocyanates with anNCO content of about 23% by weight, 40 parts by weight of an emulsion ofpoly(alkali metal silicate-unsaturated compound-epoxide compound)copolymer as produced in the examples listed below, 20 parts by weightof a polyol listed below, 5 parts by weight of trichlorotrifluoroethane,2 parts by weight of methylene chloride, 1 part by weight of a siliconesurfactant (L-5740 produced by Union Carbide), 0.05 parts by weight oftriethylamine and 0.005 parts by weight of tin laurate are thoroughlymixed. The mixture begins to expand in 15 seconds to 3 minutes therebyproducing a foamed polyurethane silicate resinous product.

    ______________________________________                                             EMULSION                                                                 EX-  PRO-                                                                     AM-  DUCED IN                                                                 PLE  EXAMPLE    POLYOL                                                        ______________________________________                                        a    Example 1  Ethylene glycol (mol. wt. 600)                                b    Example 2  Propylene glycol (mol. wt. 600)                               c    Example 3  Propylene glycol (mol. wt. 1200)                              d    Example 4  Sucrose amine polyol with a hydroxyl                                          No. 530 and viscosity of 11,000 (cps)                         e    Example 5  Polyethylene triol with a hydroxyl No. 56,                                    2000 mol wt.                                                  f    Example 6  Phenolic based polyol,                                                        hydroxyl No. 515-545,                                                         viscosity of 20,000-25,000.                                   g    Example 7  powdered wood                                                 h    Example 8  powdered bark                                                 i    Example 9  polybutadiene polymer                                                         containing OH groups                                                          (Poly bd R-45M produced by ARCO)                              j    Example 10 Polyester resin terminated in OH groups                       k    Example 11 polyethylene diol and mol wt. 1000.                           ______________________________________                                    

EXAMPLE 22

Example 21 is modified by adding about 200 parts by weight of awater-binding agent, Portland Cement to the mixture thereby producing afoamed polyurethane silicate concrete product.

Other water-binding agents may be used in place of Portland Cement suchas other hydraulic cements, gypsum, burnt lime, synthetic anhydrites andmixtures thereof.

EXAMPLE 23

Example 20 is modified wherein an amount of Portland cement equal to theweight of the isocyanate-terminated polyurethane prepolymer is added tothe mixture with the other components thereby producing a polyurethanesilicate resinous concrete product.

Other water-binding agents may be used in place of Portland Cement suchas other hydraulic cements, gypsum, burnt lime, synthetic anhydrites andmixtures thereof.

The polyurethane silicate resinous concrete may be used to producebuilding panels.

EXAMPLE 24

Example 14 is modified wherein 50 parts by weight of Portland Cement isadded to the stable emulsion and thoroughly mixed then poured into aclosed mold and within 24 hours a poly(sodium silicatebutadiene-propylene oxide) copolymer reinforced concrete is produced.

EXAMPLE 25

About 50 parts by weight of the emulsion of poly(sodium silicate-allylchloride-isoprene-vinylidene-propylene oxide) copolymer as produced inExample 17, 50 parts by weight of water, 150 parts by weight of Portlandcement and 150 parts by weight of plaster's sand are thoroughly mixedthen poured into a building block mold and is cured thereby producing aninorganic-organic plaster reinforced building block.

EXAMPLE 26

About 20 parts by weight of the emulsion of poly(sodiumsilicate-styrene-propylene oxide) copolymer as produced in Example 2, 30parts by weight of water and 100 parts by weight of gypsum arethoroughly mixed then poured into a mold of an art object therebyproducing an inorganic-organic plastic reinforced art object.

EXAMPLE 27

About 50 parts by weight of an aqueous sodium silicate containing about10% by weight of Na₂ O and 15% by weight of SiO₂, 2 parts by weight ofadipic acid, 10 parts by weight of methyl methacrylate, 5 parts byweight of propylene oxide, 1 part by weight of sodium salt of fattyacids, 3 parts by weight of sodium hydroxide, 0.1 part by weight ofpotassium persulfate, 0.01 part by weight of benzoyl peroxide and 0.005parts by weight of ferric sulfate are thoroughly mixed to produce astable emulsion then poured into a closed system then 15 parts by weightof ethylene are slowly added while agitated for 30 to 120 minutes atambient to 60 psiq and ambient temperature. The mixture is then heatedto 80° to 100° C. while agitating. The reaction is complete within 24hours thereby producing an emulsion of poly(sodiumsilicate-ethylene-methyl methacrylate-propylene oxide) copolymer.

The emulsion may be painted on wood for a coating agent.

EXAMPLE 28

About 50 parts by weight of an aqueous sodium silicate solutioncontaining about 10% Na₂ O and 15% SiO₂, 5 parts by weight of propyleneoxide, 10 parts by weight of styrene, 0.5 parts by weight of potassiumsalt of fatty acids, 0.1 part by weight of potassium persulfate, 0.01parts by weight of ferric sulfate, 2 parts by weight of adipic acid, and0.01 parts by weight of benzoyl peroxide are thoroughly mixed therebyproducing a stable emulsion. About 10 parts by weight of propylene areslowly added while agitating at ambient pressure to 60 psiq in a closedsystem at ambient temperature for 30 to 120 minutes. The mixture is thenheated to 80° to 100° C. while agitating for 10 to 30 minutes. Thereaction is complete within 1 to 24 hours thereby producing an emulsionof poly(sodium silicate-propylene-styrene-propylene oxide) copolymer.

The emulsion may be reacted with a polyisocyanate to produce a foamedproduct which may be used for sound and thermal insulation.

Although specific conditions and ingredients have been described inconjunction with the above examples of preferred embodiments these maybe varied, and other reagents and additives may be used where suitable,as described above, with similar results.

Other modifications and applications of this invention will occur tothose skilled in the art upon reading this disclosure. These areintended to be included within the scope of this invention, as definedin the appended claims.

I claim:
 1. The process of the production of alkali metalsilicate-organic plastic by mixing and reacting the followingcomponents:(a) an aqueous alkali metal silicate solution in the amountof 100 parts by weight (b) a polymerable unsaturated organic compound inthe amount of 5 to 100 parts by weight (c) a mono or polycarboxylic acidsalt forming compound in the amount of 1 to 10 parts by weight (d) anorganic epoxide compound selected from the group consisting of ethyleneoxide, propylene oxide, epichlorohydrin and mixtures thereof in theamount of 1 to 50 parts by weight (e) an initiator, a catalytic amount.2. The process of claim 1 wherein the alkali metal silicate is selectedfrom the group consisting of sodium silicate, potassium silicate andmixtures thereof.
 3. The process of claim 1 wherein the polymerableunsaturated organic compound is selected from the group consisting ofvinyl monomers, organic dienes, allyl compounds, unsaturated aliphatichydrocarbon compounds, and mixtures thereof.
 4. The process of claim 1wherein the salt forming compound is selected from the group consistingof aliphatic carboxylic acid, aliphatic polycarboxylic acid,cycloaliphatic carboxylic acid, cycloaliphatic polycarboxylic acid,heterocyclic polycarboxylic acid, aromatic carboxylic acid, aromaticpolycarboxylic acid, aliphatic carboxylic acid anhydride, aromaticcarboxylic acid anhydride and mixtures thereof.
 5. The process of claim1 wherein the organic acid is adipic acid.
 6. The process of claim 1wherein the initiator is selected from the group consisting of organicperoxide, inorganic peroxide, alkali metal persulfate, ammoniumpersulfate, a redox system and a peroxide with a metal catalyst.
 7. Theprocess of claim 1 wherein inorganic or organic particulates orpulverulent materials are added to the reaction mixture.
 8. The processof claim 3 wherein the vinyl monomer is selected from the groupconsisting of acrylate compounds, styrene, vinyl acetate, vinylchloride, vinylidine chloride, acrylonitrile, vinyl toluenes, N-vinylcarbozole, vinyl pyrovidone, vinylidine cyanide, alkyl vinyl ketones,aryl vinyl ketones, methacrylonitrile and mixtures thereof.
 9. Theprocess of claim 3 wherein the allyl compound is selected from the groupconsisting of isoprene, chloroprene, butadiene and mixtures thereof. 10.The process of claim 3 wherein the allyl compound is selected from thegroup consisting of allyl alcohol, 3-chloropropene, 3-bromopropene,methallyl chloride and mixtures thereof.
 11. The process of claim 3wherein unsaturated organic aliphatic hydrocarbons is selected from thegroup consisting of ethylene, propylene and mixtures thereof.
 12. Theprocess of claim 1 wherein a water-binding agent selected from the groupconsisting of hydraulic cement, gypsum, burnt lime, synthetic anhydriteand mixtures thereof, in the amount of 1 to 300 parts by weight and upto 400 parts by weight of a filler are added to the mixture ofcomponents (a), (b), (c), (d) and (e) thereby producing aninorganic-organic concrete.
 13. The process of claim 1 wherein awater-binding agent selected from the group consisting of hydrauliccement, gypsum, burnt lime, synthetic anhydrite and mixtures thereof, inthe amount of 1 to 300 parts by weight and up to 400 parts by weight ofa filler are added to and mixed with the alkali metal silicate organicplastic thereby producing an inorganic-organic concrete.
 14. The productproduced by the process of claim
 1. 15. The product produced by theprocess of claim
 13. 16. The product produced by the process of claim12.
 17. The process of claim 1 wherein up to 10% by weight of an epoxidestarting compound which contains a reactive hydrogen atom, is added withthe components, percentage based on the reactants (a), (b), (c), and(d).